Method of forming topology-controlled amorphous carbon polymer film

ABSTRACT

A method of forming a topology-controlled layer on a patterned recess of a substrate, includes: (i) depositing a Si-free C-containing film having filling capability on the patterned recess of the substrate by pulse plasma-assisted deposition to fill the recess in a bottom-up manner or bottomless manner; and (ii) subjecting the bottom-up or bottomless film filled in the recess to plasma aching to remove a top portion of the filled film in a manner leaving primarily or substantially only a bottom portion of the filled film or primarily or substantially only a sidewall portion of the filled film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 62/876,588, filed on Jul. 19, 2019, in the United States Patent and Trademark Office, the disclosure of which is incorporated herein in its entirety by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention generally relates to a method of forming a topology-controlled amorphous carbon film on a patterned recess of a substrate.

Description of the Related Art

In processes of fabricating integrated circuits such as those for shallow trench isolation, inter-metal dielectric layers, passivation layers, etc., it is often necessary to fill trenches (any recess typically having an aspect ratio of one or higher) with insulating material. However, with miniaturization of wiring pitch of large scale integration (LSI) devices, void-free filling of high aspect ratio spaces (e.g., AR≥3) becomes increasingly difficult due to limitations of existing deposition processes.

In view of the above, the present inventor developed a gap-fill technology for deposition of flowable film and disclosed the technology in U.S. patent application Ser. No. 16/026,711, filed Jul. 3, 2018, which provides complete gap-filling by plasma-assisted deposition using a hydrocarbon precursor substantially without formation of voids under conditions where a nitrogen, oxygen, or hydrogen plasma is not required, the disclosure of which is herein incorporated by reference in its entirety.

However, if a certain application, where a sacrificial etch stop layer or protection layer, for example, is necessary only at the bottom of a recess, requires bottom-only deposition of amorphous carbon using the above gap-fill technology in trenches of a substrate, there might be the following issues: i) a certain amount of film (although it is small but not negligible) may be deposited on the top face of the substrate; ii) the amount of film deposited at the bottom of each trench may be irregular depending on the structure volume of each trench (see (a) of FIG. 8); and iii) even when the structure volume of each trench is similar, there may be some randomness in gap-filling (see (b) of FIG. 8). The present inventor provides herein a solution to the above issues.

In other applications such as 3D NAND flash, ultradeep hole straight etching is required. However, it is very difficult to maintain the straight structure as is due to the occurrence of sidewall etching during the hole etching, resulting in lowering CD integrity. The present inventor has discovered that the above gap-fill technology can provide a solution to the above problem.

Any discussion of problems and solutions involved in the related art has been included in this disclosure solely for the purposes of providing a context for the present invention, and should not be taken as an admission that any or all of the discussion were known at the time the invention was made.

SUMMARY OF THE INVENTION

In view of the above, some embodiments provide a method of forming a topology-controlled layer on a patterned recess of a substrate, comprising: (i) depositing a Si-free C-containing film having filling capability on the patterned recess of the substrate by pulse plasma-assisted deposition to fill the recess in a bottom-up manner or bottomless manner; and (ii) subjecting the bottom-up or bottomless film filled in the recess to plasma ashing to remove a top portion of the filled film in a manner leaving primarily only a bottom portion of the filled film or primarily only a sidewall portion of the filled film. According to the above embodiments, by using the gap-fill technology, the topology of the film can be manipulated. The degree of flowability of film relative to the size of the trench can primarily determine whether deposition is bottom-up deposition or bottomless deposition.

When the flowability of film is sufficiently high relative to target trenches, bottom-up deposition occurs, and after completely filling the trenches and further depositing film above the trenches, by subjecting the film to plasma ashing, the top portion of the film above the trenches as well as an upper portion of film filled in the trenches can equally be removed to a uniform depth of the trenches so as to obtain trenches filled with film having substantially a uniform depth.

When the flowability of film is sufficiently low relative to target trenches, bottomless deposition occurs; however, because the film is flowable, even when the film does not reach the bottom of the trench and closes the upper opening of the trench, the film can deposit along the sidewall of the trench to cover the sidewall to a certain depth from the top surface of the substrate. After completion of deposition of the film, by subjecting the film to plasma ashing, the portion of the film closing the opening of the trench can be removed to open the trench, leaving the sidewall film as a spacer. Thereafter, ultradeep hole straight etching can be performed. Since the bottom of the trench is substantially not covered by the film, and the sidewall film can protect the sidewall from being etched during the ultradeep hole straight etching, etching can progress in the depth direction to form an ultradeep straight hole, without degrading CD integrity.

For purposes of summarizing aspects of the invention and the advantages achieved over the related art, certain objects and advantages of the invention are described in this disclosure. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.

Further aspects, features and advantages of this invention will become apparent from the detailed description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features of this invention will now be described with reference to the drawings of preferred embodiments which are intended to illustrate and not to limit the invention. The drawings are greatly simplified for illustrative purposes and are not necessarily to scale.

FIG. 1A is a schematic representation of a PEALD (plasma-enhanced atomic layer deposition) apparatus for depositing a dielectric film usable in an embodiment of the present invention.

FIG. 1B illustrates a schematic representation of a precursor supply system using a flow-pass system (FPS) usable in an embodiment of the present invention.

FIG. 2 is a chart illustrating schematic cross sectional views of trenches subjected to bottom-up deposition ((a)→(b)→(c)), and bottomless deposition ((a)→(d)→(e)) according to embodiments of the present invention.

FIG. 3 shows STEM photographs of cross-sectional views of trenches subjected to bottom-up deposition in (a), followed by O₂/Ar ashing in (b) or by N₂/H₂ ashing in (c) according to embodiments of the present invention.

FIG. 4 shows a schematic illustration of a STEM photograph of a cross-sectional view of a trench subjected to bottomless deposition (300 cycles) without ashing

FIG. 5 shows a schematic illustration of a STEM photographs of a cross-sectional view of a trench subjected to bottomless deposition (300 cycles), followed by ashing (90 seconds) according to an embodiment of the present invention.

FIG. 6 shows a schematic illustration of a STEM photograph of a cross-sectional view of a trench subjected to bottomless deposition (350 cycles) without ashing.

FIG. 7 shows a schematic illustration of a STEM photograph of a cross-sectional view of a trench subjected to bottomless deposition (350 cycles), followed by ashing (90 seconds) according to an embodiment of the present invention.

FIG. 8 shows STEM photographs of cross-sectional views of trenches subjected to bottom-up deposition, wherein (a) represents trenches having different widths, and (b) represents trenches filled with irregular amount of film.

FIG. 9 shows STEM photographs of cross-sectional views of trenches subjected to bottom-up deposition, wherein (a) represents trenches at completion of deposition, and (b) represents the trenches after ashing according to an embodiment of the present invention.

FIG. 10 shows STEM photographs of cross-sectional views of trenches subjected to bottom-up deposition (full fill), wherein raw (a) represents a mixture of wide trenches and narrow trenches having different widths (the scale represents 300 nm), raw (b) represents intermediate trenches (the scale represents 60 nm), and raw (c) represents wide trenches with slight difference in width (the scale represents 60 nm), column (1) represents the trenches with full-fill deposition (210 cycles of deposition) prior to ashing, column (2) represents the trenches after ashing for 105 seconds, column (3) represents the trenches after ashing for 129 seconds, and column (4) represents the trenches after ashing for 165 seconds, according to an embodiment of the present invention.

FIG. 11 shows STEM photographs of cross-sectional views of trenches subjected to bottom-up deposition, wherein (a) represents trenches at completion of full-fill deposition (210 cycles of deposition), (b) represents the trenches after ashing for 240 seconds, and (c) represents the trenches after ashing for 300 seconds, according to an embodiment of the present invention.

FIG. 12 is a chart illustrating the sequence of processes of film formation according to an embodiment of the present invention, wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each column does not represent duration of each process.

DETAILED DESCRIPTION OF EMBODIMENTS

In this disclosure, “gas” may include vaporized solid and/or liquid and may be constituted by a single gas or a mixture of gases, depending on the context. Likewise, an article “a” or “an” refers to a species or a genus including multiple species, depending on the context. In this disclosure, a process gas introduced to a reaction chamber through a showerhead may be comprised of, consist essentially of, or consist of a silicon-free hydrocarbon precursor and an additive gas. The additive gas may include a plasma-generating gas for exciting the precursor to form an amorphous carbon polymer when RF power is applied to the additive gas. The additive gas may be an inert gas which may be fed to a reaction chamber as a carrier gas and/or a dilution gas. The additive gas may contain no reactant gas for oxidizing or nitriding the precursor. Alternatively, the additive gas may contain a reactant gas for oxidizing or nitriding the precursor to the extent not interfering with plasma polymerization forming an amorphous carbon-based polymer. Further, in some embodiments, the additive gas contains only a plasma-generating gas (e.g., noble gas). The precursor and the additive gas can be introduced as a mixed gas or separately to a reaction space. The precursor can be introduced with a carrier gas such as a rare gas. A gas other than the process gas, i.e., a gas introduced without passing through the showerhead, may be used for, e.g., sealing the reaction space, which includes a seal gas such as a rare gas. In some embodiments, the term “precursor” refers generally to a compound that participates in the chemical reaction that produces another compound, and particularly to a compound that constitutes a film matrix or a main skeleton of a film, whereas the term “reactant” refers to a compound, other than precursors, that activates a precursor, modifies a precursor, or catalyzes a reaction of a precursor, wherein the reactant may provide an element (such as O, C, N) to a film matrix and become a part of the film matrix, when in an excited state. The term “plasma-generating gas” refers to a compound, other than precursors and reactants, that generates a plasma when being exposed to electromagnetic energy, wherein the plasma-generating gas may not provide an element (such as O, C, N) to a film matrix which becomes a part of the film matrix. The term “plasma-aching gas” refers to a gas which ashes a film when in a state excited either directly (direct plasma) or remotely (remote plasma). In some embodiments, the “plasma-aching gas” is a single gas or a mixed gas of two or more gases. The term “aching” refers to removal of organic matter using a plasma, leaving mineral components behind as a residue (ash) which is typically removed with a vacuum pump.

In some embodiments, “film” refers to a layer continuously extending in a direction perpendicular to a thickness direction substantially without pinholes to cover an entire target or concerned surface, or simply a layer covering a target or concerned surface. In some embodiments, “layer” refers to a structure having a certain thickness formed on a surface or a synonym of film or a non-film structure. A film or layer may be constituted by a discrete single film or layer having certain characteristics or multiple films or layers, and a boundary between adjacent films or layers may or may not be clear and may be established based on physical, chemical, and/or any other characteristics, formation processes or sequence, and/or functions or purposes of the adjacent films or layers. Further, in this disclosure, any two numbers of a variable can constitute a workable range of the variable as the workable range can be determined based on routine work, and any ranges indicated may include or exclude the endpoints. Additionally, any values of variables indicated (regardless of whether they are indicated with “about” or not) may refer to precise values or approximate values and include equivalents, and may refer to average, median, representative, majority, etc. in some embodiments. Further, in this disclosure, the terms “constituted by” and “having” refer independently to “typically or broadly comprising”, “comprising”, “consisting essentially of”, or “consisting of” in some embodiments. In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments.

In this disclosure, “continuously” refers to without breaking a vacuum, without interruption as a timeline, without any material intervening step, without changing treatment conditions, immediately thereafter, as a next step, or without an intervening discrete physical or chemical structure between two structures other than the two structures in some embodiments.

In this disclosure, the term “filling capability” (also referred to as “flowability”) refers to a capability of filling a gap substantially without voids (e.g., no void having a size of approximately 5 nm or greater in diameter) and seams (e.g., no seam having a length of approximately 5 nm or greater), wherein seamless/voidless bottom-up growth of a layer is observed, when a film is deposited in a wide trench having an aspect ratio of about 1 or more.

The flowability is often manifested as a concave surface of a film at a bottom of a wide trench before filling the trench, and also manifested as a substantially planar top surface of a film when being continuously deposited after completely filling the trench (planarization). Such deposition is referred to as “bottom-up deposition.”

When a trench is narrow and deep, even though a film is flowable, the film may not reach a bottom of the trench. In that case, the flowability is often manifested as a roughly or substantially conformal film along sidewalls of the trench with substantially no film at a bottom of the trench and typically with a top opening of the trench closed off by a film. Since the film is flowable, the sidewall film flows and extends downward along the sidewalls, thereby forming a thin film, wherein a ratio of averaged thickness of a substantially conformal part of the film (except a top part closing the top opening of the trench, which is subsequently removed by aching) to depth of the film in the trench (length extended toward the bottom along the sidewall) may be in a range of 0.1% to 10% (typically 0.5% to 5%). Such deposition is referred to as “bottomless deposition”.

In this disclosure, a recess between adjacent protruding structures and any other recess pattern is referred to as a “trench”. That is, a trench is any recess pattern including a hole/via. For bottom-up deposition, in some embodiments, the trench has a width of about 20 nm to about 100 nm (typically about 30 nm to about 50 nm) (wherein when the trench has a length substantially the same as the width, it is referred to as a hole/via), a depth of about 30 nm to about 100 nm (typically about 40 nm to about 60 nm), and an aspect ratio of about 2 to about 10 (typically about 2 to about 5). For bottomless deposition, in some embodiments, the trench has a width (CD) of about 5.5 nm to about 200 nm (typically about 10 nm to about 100 nm), a depth of about 800 nm to about 10,000 nm (typically about 300 nm to about 8,000 nm), and an aspect ratio of about 15 to about 150 (typically about 20 to about 100). Proper dimensions of the trench may vary depending on the process conditions, flowability of the film, film compositions, intended applications, etc. By tuning the flowability of the film, for example, bottom-up deposition and bottomless deposition can be realized in trenches having sizes different from those described above.

In this disclosure, the term “substantially no deposition,” “substantially no film,” or the like refers to a quantity functionally equivalent to zero, an immaterial or negligible quantity, a quantity which does not materially interfere with subsequent processes (e.g., ashing), a quantity lower than a detectable or observable quantity, or the like.

In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments. Also, in this disclosure, “the invention” or “the present invention” refers to at least one of the embodiments or aspects explicitly, necessarily, or inherently disclosed herein.

Embodiments will be explained with respect to preferred embodiments. However, the present invention is not intended to be limited to the preferred embodiments.

Some embodiments provide a method of forming a topology-controlled layer on a patterned recess of a substrate, comprising: (i) depositing a Si-free C-containing film having filling capability on the patterned recess of the substrate by pulse plasma-assisted deposition to fill the recess in a bottom-up manner or bottomless manner; and (ii) subjecting the bottom-up or bottomless film filled in the recess to plasma ashing to remove a top portion of the filled film in a manner leaving primarily only a bottom portion of the filled film or primarily only a sidewall portion of the filled film. The Si-free C-containing film may typically be an amorphous carbon polymer film which is a flowable film. When an amorphous carbon polymer film is formed by using a plasma-assisted method, the resultant amorphous carbon polymer film is constituted by hydrogenated amorphous carbon polymer. In this disclosure, a hydrogenated amorphous carbon polymer may simply refer to an amorphous carbon polymer, which may also be referred to as “aC:H” or simply “aC” as an abbreviation. Further, in this disclosure, SiC, SiCO, SiCN, SiCON, or the like is an abbreviation indicating a film type (indicated simply by primary constituent elements) in a non-stoichiometric manner unless described otherwise.

In some embodiments, in step (i), the Si-free C-containing film is deposited using a hydrocarbon precursor. In some embodiments, step (i) comprises: (ia) supplying a precursor to a reaction space where the substrate is placed, and (ib) exposing the patterned recess of the substrate to a plasma to deposit the Si-free C-containing film in the patterned recess, wherein step (ib) is conducted intermittently in a manner pulsing the plasma, and step (ia) is conducted continuously or intermittently without overlapping step (ib) as a step prerequisite for step (ib). In some embodiments, the Si-free C-containing film is constituted substantially by hydrocarbons.

Deposition of flowable film is known in the art; however, conventional deposition of flowable film uses chemical vapor deposition (CVD) with constant application of RF power, since pulse plasma-assisted deposition such as PEALD is well known for depositing a conformal film which is a film having characteristics entirely opposite to those of flowable film. In some embodiments, flowable film is a silicon-free carbon-containing film constituted by an amorphous carbon polymer, and although any suitable one or more of hydrocarbon precursors can be candidates, in some embodiments, the precursor includes an unsaturated or cyclic hydrocarbon having a vapor pressure of 1,000 Pa or higher at 25° C. In some embodiments, the precursor is at least one selected from the group consisting of C2-C8 alkynes (C_(n)H_(2n−2)), C2-C8 alkenes (C_(n)H_(2n)), C2-C8 diene (C_(n)H_(n+2)), C3-C8 cycloalkenes, C3-C8 annulenes (C_(n)H_(n)), C3-C8 cycloalkanes, and substituted hydrocarbons of the foregoing. In some embodiments, the precursor is ethylene, acetylene, propene, butadiene, pentene, cyclopentene, benzene, styrene, toluene, cyclohexene, and/or cyclohexane.

In some embodiments, as the gap-fill technology for deposition of flowable film, the method disclosed in U.S. patent application Ser. No. 16/026,711 can be used, which provides complete gap-filling by plasma-assisted deposition using a hydrocarbon precursor substantially without formation of voids under conditions where a nitrogen, oxygen, or hydrogen plasma is not required, the disclosure of which is herein incorporated by reference in its entirety.

By changing deposition conditions or process parameters, a non-flowable film can be formed. For example, such parameters include, but are not limited to, partial pressure of precursor, deposition temperature, deposition pressure, etc. For example, by increasing the deposition temperature, decreasing the deposition pressure, and/or decreasing the precursor ratio (a ratio of precursor flow to carrier/dilution gas flow), the flowability of film becomes low. In some embodiments, process (i) (deposition process) is conducted by plasma-enhanced atomic layer deposition (PEALD) or other cyclic plasma-assisted deposition (e.g., cyclic PECVD). As a plasma, a capacitively coupled plasma, inductively coupled plasma, remote plasma, a plasma generated by RF power, a plasma generated by microwaves, etc. can be used.

In some embodiments, the plasma aching in step (ii) is conducted using a direct or remote oxygen or hydrogen plasma. In some embodiments, the direct or remote oxygen or hydrogen plasma is a direct or remote plasma of gas(es) selected from the group consisting of solely H₂, a mixture of Ar and H₂ (an Ar/H₂ flow ratio of 0.005 to 0.995, typically 0.05 to 0.75), amixture of He and H₂ (a He/H₂ flow ratio of 0.005 to 0.995, typically 0.05 to 0.75), a mixture of N₂ and H₂ (an N₂/H₂ flow ratio of 0.005 to 0.995, typically 0.05 to 0.75), solely O₂, a mixture of O₂ and Ar (an O₂/Ar flow ratio of 0.005 to 0.995, typically 0.05 to 0.75), a mixture of O₂ and He (anO₂/He flow ratio of 0.005 to 0.995, typically 0.05 to 0.75), and a mixture of O₂ and N₂ (an O₂/N₂ flow ratio of 0.005 to 0.995, typically 0.05 to 0.75).

In some embodiments, an aspect ratio of the recess is in a range of 10 to 150 (typically 15 to 100), and a depth of the recess is more than 200 nm wherein the recess is filled with the film in a bottomless manner in step (i) and a top portion of the filled film closes off a top opening of the recess. In some embodiments, plasma ashing is conducted to open the closed top portion of the recess and to leave primarily or substantially only the sidewall portion of the filled film in step (ii).

In some embodiments, the substrate has multiple recesses having aspect ratios of 2 to 30 (typically 3 to 20), wherein the recesses are filled with the film in a bottom-up manner in step (i) wherein there are variations in surface topology due to the loading effect. In some embodiments, step (i) continues until planarization of the film above the multiple recesses occurs, and plasma ashing is then conducted to make the surface topology of the film filled in the multiple recesses uniform, and to leave primarily or substantially only the bottom portion of the filled film in step (ii).

Embodiments will be explained with respect to the drawings. However, the present invention is not intended to be limited to the drawings.

FIG. 2 is a chart illustrating schematic cross sectional views of trenches subjected to bottom-up deposition ((a)→(b)→(c)), and bottomless deposition ((a)→(d)→(e)) according to embodiments of the present invention. First, in (a) of FIG. 2, a substrate with trenches is provided, wherein for bottom-up deposition, a substrate 21 has a trench 20 having a width which is sufficiently wide to allow a flowable film to flow into the trench, and having a depth which is sufficiently small to allow the flowable film to reach a bottom of the trench 20, whereas for bottomless deposition, a substrate 31 has a trench 30 having a width which is sufficiently wide to allow a flowable film to flow into the trench but sufficiently narrow to clog the top opening of the trench 30 with the film before the film reaches a bottom of the trench 30, and having a depth which is sufficiently large to disallow the flowable film to reach a bottom of the trench 30. Suitable sizes of trenches, by way of example, are described in this disclosure and can be selected according to the flowability of the film, for example. It should be noted that FIG. 2 is overly simplified and is not scaled.

Next, in the deposition process, the same process conditions of deposition can be used for both bottom-up deposition in (b) and bottomless deposition in (d), except for the number of deposition cycles, the duration of ashing, etc. which are modified depending on the size of trenches, the target deposition thickness of the film, the target ashing quantity, the target final topology of the film, etc. In (b), the flowable film fills the trench 20 in a bottom-up manner and continuously deposits on the substrate 21 after completely filling the trench 20, until a top surface of the film 22 is planarized. Planarization can be achieved due to the flowability of the film. In (d), the flowable film deposits on a top of the substrate 31 and flows into the trench 30, moving downward along sidewalls of the trench 30 in a bottomless manner, while clogging the top opening of the trench 30 with the flowable film 32. Since the flowable film flows downward along the sidewall of the trench 30 having an aspect ratio of about 10 to 100, for example, the film on the sidewall becomes substantially conformal along the sidewall, which can serve as a spacer. It should be noted that the bottom-up deposition and the bottomless deposition can be conducted on trenches having the same size, by tuning the flowability of film for each deposition. For example, the method of tuning the flowability disclosed in U.S. patent application Ser. No. 16/026,711 can be used.

Next, in the aching process, the amorphous carbon constituting the film is removed (ached) from the top surface exposed to a plasma to a depth suitable for bottom-only topology or sidewall-only topology. In (c), by removing the portion of the film 22 deposited on the top surface of the substrate 21 and an upper portion of the film 22 filled in the trench 20 in a bottom-up manner, a film 23 having bottom-only topology can be obtained, which is homogenous and has substantially a uniform depth. In (e), by removing the portion of the film 32 deposited on the top surface of the substrate 31 and an upper portion of the film 32 closing the upper opening of the trench 30 in a bottomless manner, a film 33 having sidewall-only topology can be obtained, which is homogenous and has substantially a uniform thickness.

In some embodiments, preferably, the deposition process uses ALD-like recipes (e.g., feed/purge/plasma strike/purge) wherein the purge after feed is voluntarily severely shortened to leave high partial pressure of precursor during the plasma strike, as disclosed in U.S. patent application Ser. No. 16/026,711. This is clearly distinguished from ALD chemistry or mechanism. The above processes can be based on pulse plasma CVD which also imparts good filling capabilities to resultant films although the ALD-like recipes may be more beneficial as discussed later.

In some embodiments, the critical aspects for flowability of depositing film, different from conventional ALD, include:

1) High-enough partial pressure during the entire RF-ON period for polymerization/chain growth to progress;

2) Sufficient energy to activate the reaction (defined by the RF-ON period and RF power), a not overly long RF-ON period; and

3) Temperature and pressure for polymerization/chain growth set above a melting point of flowable phase but below a boiling point of the deposited material.

In some embodiments, process parameter ranges are adjusted as follows for tuning the flowability of film:

TABLE 1 (numbers are approximate) Low ← Viscosity → High Partial pressure of precursor (Pa) >50 (preferably, >200) Wafer temperature (° C.) −10 to 200 (preferably, 50 to 150) Total pressure (Pa) 300 to 101325 (preferably, >500)

As for pressure, high pressure is preferable for flowability, since gravity and surface tension are the driving force for the film to flow at the bottom. As for temperature, low temperature is preferable for flowability (this is much less intuitive), although high temperature favors the polymer chain growth rate.

FIG. 12 is a chart illustrating the sequence of processes of film formation according to an embodiment of the present invention, wherein a cell in gray represents an ON state whereas a cell in white represents an OFF state, and the width of each column does not represent duration of each process. This simplified process sequence can be adopted to both bottom-up deposition and bottomless deposition, and in some embodiments, the same process conditions of deposition can be used for both bottom-up deposition and bottomless deposition, except for the number of deposition cycles, the duration of ashing, etc. which are modified depending on the size of trenches, the target deposition thickness of the film, the target ashing quantity, the target final topology of the film, etc.

This process sequence comprises a deposition process (“Feed” →“Purge” →“RF Pulse-1” (plasma polymerization)→“Purge”), and a plasma ashing process (“Stabilize” →“RF Pulse-2” (plasma ashing)→“Purge”). The plasma polymerization process comprises depositing an amorphous carbon polymer film on a substrate having trenches by PEALD-like deposition using a Si- and metal-free, C-containing precursor and a plasma-generating gas which generates a plasma by applying RF power (RF) between two electrodes between which the substrate is placed in parallel to the two electrodes, wherein RF power is applied in each sublayer deposition cycle of PEALD-like deposition, wherein the plasma-generating gas and the carrier gas flow continuously and function also as a purging gas during “Purge” after “Feed” and during “Purge” after “RF Pulse-1”.

In some embodiments, the feed time is in a range of 0.3 to 10 seconds (typically 0.6 to 2 seconds), the purge time after the feed is in a range of 0 to 0.5 seconds (typically 0 to 0.3 seconds), the RF time is in a range of 0.5 to 2 seconds (typically 0.8 to 1.5 seconds), the purge time after the RF is in a range of 0 to 0.5 seconds (typically 0 to 0.1 seconds), the carrier gas flow is in a range of 0 to 0.8 slm (typically 0.1 to 0.3 slm), the plasma-generating gas flow is in a range of 0 to 0.5 slm (typically 0.1 to 0.3 slm), and the RF power is in a range of 50 to 400 W (typically 75 to 200 W) for a 300-mm wafer (for different size wafers, the above wattage is applied as W per unit area (cm²) of each wafer).

The flowability of film is temporarily obtained when a volatile hydrocarbon precursor, for example, is polymerized by a plasma and deposited on a surface of a substrate, wherein gaseous monomer (precursor) is activated or fragmented by energy provided by plasma gas discharge so as to initiate polymerization, and when the resultant polymer material is deposited on the surface of the substrate, the material shows temporarily flowable behavior. When the deposition step is complete, the flowable film is no longer flowable but is solidified, and thus, a separate solidification process is not required.

The deposition process is a PEALD-like process, one cycle of which for forming a sublayer (typically thicker than a monolayer) may be repeated at q times until a desired thickness of the amorphous carbon polymer film is obtained before starting the plasma ashing process, wherein q is an integer of 5 to 100 (preferably 25 to 50) for the bottom-up deposition, depending on the size of the trenches, the intended use of the film, etc., so as to deposit the amorphous carbon polymer film having a thickness of 2.5 nm to 50 nm (preferably 7.5 nm to 25 nm) above the top surface of the substrate before starting the plasma ashing process; and wherein q is an integer of 10 to 200 (preferably 40 to 100) for the bottomless deposition, depending on the size of the trenches, the intended use of the film, etc., so as to deposit the amorphous carbon polymer film having a thickness of 5 nm to 100 nm (preferably 20 nm to 50 nm) above the top surface of the substrate before starting the plasma ashing process.

Next, the plasma ashing process begins, which comprises feeding an ashing gas (H₂ or O₂, or a mixture of the foregoing and N₂, Ar, and/or He) to the reaction space (“Stabilize”) which is excited by RF power (RF) to generate a plasma and ash the amorphous carbon polymer film (“RF Pulse-2”), followed by purging (“Purge”), wherein the ashing gas is fed continuously to the reaction space throughout the plasma ashing process. In some embodiments, the RF power for the plasma ashing is in a range of 50 to 500 W (typically 50 to 200 W) under a pressure of 100 Pa to 1000 Pa (typically 200 to 600 Pa) for a duration of 5 to 200 seconds (typically 10 to 100 seconds), the stabilization time is in a range of 5 to 60 seconds (typically 10 to 30 seconds), the purge time after the RF is in a range of 5 to 60 seconds (typically 10 to 30 seconds), and the ashing gas flow is in a range of 0.1 to 10 slm (typically 0.5 to 2 slm).

In some embodiments, throughout the entirety of the processes, the carrier gas is fed continuously to the reaction space in a range of 0 sccm to 2000 sccm (preferably 100 sccm to 500 sccm), for example. Also, the temperature of the processes may be in a range of −50° C. to 175° C. (preferably 35° C. to 150° C.).

The plasma-generating gas in the deposition process and the ashing gas in the plasma ashing process can be the same or different, e.g., both can be Ar and/or He.

The continuous flow of the carrier gas can be accomplished using a flow-pass system (FPS) wherein a carrier gas line is provided with a detour line having a precursor reservoir (bottle), and the main line and the detour line are switched, wherein when only a carrier gas is intended to be fed to a reaction chamber, the detour line is closed, whereas when both the carrier gas and a precursor gas are intended to be fed to the reaction chamber, the main line is closed and the carrier gas flows through the detour line and flows out from the bottle together with the precursor gas. In this way, the carrier gas can continuously flow into the reaction chamber, and can carry the precursor gas in pulses by switching between the main line and the detour line. FIG. 1B illustrates a precursor supply system using a flow-pass system (FPS) according to an embodiment of the present invention (black valves indicate that the valves are closed). As shown in (a) in FIG. 1B, when feeding a precursor to a reaction chamber (not shown), first, a carrier gas such as Ar (or He) flows through a gas line with valves b and c, and then enters a bottle (reservoir) 26. The carrier gas flows out from the bottle 26 while carrying a precursor gas in an amount corresponding to a vapor pressure inside the bottle 26, and flows through a gas line with valves f and e, and is then fed to the reaction chamber together with the precursor. In the above, valves a and d are closed. When feeding only the carrier gas (noble gas) to the reaction chamber, as shown in (b) in FIG. 1B, the carrier gas flows through the gas line with the valve a while bypassing the bottle 26. In the above, valves b, c, d, e, and f are closed.

The process cycle can be performed using any suitable apparatus including an apparatus illustrated in FIG. 1A, for example. FIG. 1A is a schematic view of a PEALD apparatus, desirably in conjunction with controls programmed to conduct the sequences described below, usable in some embodiments of the present invention. In this figure, by providing a pair of electrically conductive flat-plate electrodes 4, 2 in parallel and facing each other in the interior 11 (reaction zone) of a reaction chamber 3, applying HRF power (13.56 MHz or 27 MHz) 25 to one side, and electrically grounding the other side 12, a plasma is excited between the electrodes. A temperature regulator is provided in a lower stage 2 (the lower electrode), and a temperature of a substrate 1 placed thereon is kept constant at a given temperature. The upper electrode 4 serves as a shower plate as well, and reactant gas and/or dilution gas, if any, and precursor gas are introduced into the reaction chamber 3 through a gas line 27 and a gas line 28, respectively, and through the shower plate 4. Additionally, in the reaction chamber 3, a circular duct 13 with an exhaust line 7 is provided, through which gas in the interior 11 of the reaction chamber 3 is exhausted. Additionally, a transfer chamber 5 disposed below the reaction chamber 3 is provided with a seal gas line 24 to introduce seal gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5 wherein a separation plate 14 for separating the reaction zone and the transfer zone is provided (a gate valve through which a wafer is transferred into or from the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust line 6. In some embodiments, the deposition of multi-element film and surface treatment are performed in the same reaction space, so that all the steps can continuously be conducted without exposing the substrate to air or other oxygen-containing atmosphere.

In some embodiments, in the apparatus depicted in FIG. 1A, the system of switching flow of an inactive gas and flow of a precursor gas illustrated in FIG. 1B (described earlier) can be used to introduce the precursor gas in pulses without substantially fluctuating pressure of the reaction chamber.

A skilled artisan will appreciate that the apparatus includes one or more controller(s) (not shown) programmed or otherwise configured to cause the deposition and reactor cleaning processes described elsewhere herein to be conducted. The controller(s) are communicated with the various power sources, heating systems, pumps, robotics, and gas flow controllers, or valves of the reactor, as will be appreciated by the skilled artisan.

In some embodiments, a dual chamber reactor (two sections or compartments for processing wafers disposed close to each other) can be used, wherein a reactant gas and a noble gas can be supplied through a shared line whereas a precursor gas is supplied through unshared lines.

The film having filling capability can be applied to various semiconductor devices including, but not limited to, cell isolation in 3D cross point memory devices, self-aligned Via, dummy gate (replacement of current poly Si), reverse tone patterning, PC RAM isolation, cut hard mask, and DRAM storage node contact (SNC) isolation.

EXAMPLES

In the following examples where conditions and/or structures are not specified, the skilled artisan in the art can readily provide such conditions and/or structures, in view of the present disclosure, as a matter of routine experimentation. A skilled artisan will appreciate that the apparatus used in the examples included one or more controller(s) (not shown) programmed or otherwise configured to cause the deposition and reactor cleaning processes described elsewhere herein to be conducted. The controller(s) were communicated with the various power sources, heating systems, pumps, robotics and gas flow controllers or valves of the reactor, as will be appreciated by the skilled artisan.

Reference Example 1 (FIG. 3)

An amorphous carbon polymer film was deposited on a Si substrate (having a diameter of 300 mm and a thickness of 0.7 mm) having trenches with an opening of approximately 25 to 35 nm, which had a depth of approximately 85 nm (an aspect ratio was approximately 2.4 to 3.4), by PEALD-like process in a bottom-up manner according to the process sequence shown in FIG. 12 under the conditions shown in Table 2 below using the apparatus illustrated in FIG. 1A and a gas supply system (FPS) illustrated in FIG. 1B. The films were deposited to fully fill the trenches and further accumulate thereon, forming a planar top surface. PEALD-like cycles were repeated 242 times (p=242). Thereafter, aching was continuously conducted using a mixture of O₂ and Ar or a mixture of N₂ and H₂ according to the process sequence shown in FIG. 12 under the conditions shown in Table 2 below.

TABLE 2 (numbers are approximate) Temp. SUS temp (° C.). 75 setting SHD temp (° C.) 50 Wall temp (° C.) 75 BLT temp (° C.) RT Depo Pressure (Pa) 1160 Gap (mm) 16.5 Feed time (s) 0.4 Purge (s) 0.1 RF time (s) 1.5 Purge (s) 0.1 RF power (W) 230 Precursor Cyclopentene Carrier He Carrier flow (slm) 0.1 Dry He (slm) 0.2 Seal He (slm) 0.1 Ashing Stabilization (s). 15 Purge (s) 10 RF time (s) 10-300 RF power (W) 50-200 Ashing gas O₂/Ar (slm) 0.5/0.5 Ashing gas N₂/H₂ (slm) 0.5/0.5

FIG. 3 shows STEM photographs of cross-sectional views of the trenches subjected to bottom-up deposition in (a), followed by O₂/Ar ashing in (b) or by N₂/H₂ ashing in (c). As shown in FIG. 3, it was confirmed that the amorphous carbon polymer film was effectively flowable and fully filled all the trenches (regardless of the size differences) and further accumulated thereon, forming a planar top surface, and by the ashing process, the amorphous carbon polymer film could fully be removed or ached without degrading CD integrity, i.e., by manipulating the ashing time, a desired amount of amorphous carbon polymer film can be removed without degrading CD integrity.

Example 1

An amorphous carbon polymer film was deposited on a Si substrate (having a diameter of 300 mm and a thickness of 0.7 mm) having trenches with an opening of approximately 20 nm, which had a depth of approximately 200 nm (an aspect ratio was approximately 10), by PEALD-like process in a bottom-up manner under the same conditions as in Reference Example 1 except that the deposition cycle was repeated 210 times (p=210) so that the film accumulated on the top surface of the substrate to a thickness of 100 nm. Thereafter, ashing was continuously conducted using a mixture of O₂ and Ar in the same manner as in Reference Example 1 except that RF time was shortened to 90 seconds so as to form film structures having bottom-only topology wherein the film was ashed to a depth of 181 nm from the top surface of the substrate.

FIG. 9 shows STEM photographs of cross-sectional views of the trenches subjected to the bottom-up deposition, wherein (a) represents trenches at completion of deposition, and (b) represents the trenches after ashing. As shown in FIG. 9, it was confirmed that the amorphous carbon polymer film was effectively flowable and fully filled all the trenches and further accumulated thereon, forming a planar top surface, and by the ashing process, the amorphous carbon polymer film could be removed or ashed uniformly in all the trenches without degrading CD integrity, forming homogenous film structures having uniform bottom-only topology.

Example 2

An amorphous carbon polymer film was deposited on a Si substrate having trenches in the same manner as in Example 1 except that ashing time varied.

FIG. 10 shows STEM photographs of cross-sectional views of the trenches subjected to bottom-up deposition (full fill), wherein raw (a) represents a mixture of wide trenches and narrow trenches having different widths (the scale represents 300 nm), raw (b) represents intermediate trenches (the scale represents 60 nm), and raw (c) represents wide trenches with slight difference in width (the scale represents 60 nm), column (1) represents the trenches with full-fill deposition (210 cycles of deposition) prior to ashing, column (2) represents the trenches after ashing for 105 seconds, column (3) represents the trenches after ashing for 129 seconds, and column (4) represents the trenches after ashing for 165 seconds.

FIG. 11 shows STEM photographs of cross-sectional views of the trenches subjected to bottom-up deposition, wherein (a) represents trenches at completion of full-fill deposition (210 cycles of deposition), (b) represents the trenches after ashing for 240 seconds, and (c) represents the trenches after ashing for 300 seconds.

As shown in FIGS. 10 and 11, it was confirmed that the amorphous carbon polymer film was effectively flowable and fully filled all the trenches and further accumulated thereon, forming a planar top surface, and by the ashing process, the amorphous carbon polymer film could be removed or ached uniformly in all the trenches without degrading CD integrity, forming homogenous film structures having uniform bottom-only topology. Also it was confirmed that surprisingly a combination of full-fill deposition and ashing could homogenously accomplish bottom-only deposition substantially without the loading effect.

Reference Example 2

An amorphous carbon polymer film was deposited on a Si substrate (having a diameter of 300 mm and a thickness of 0.7 mm) having trenches with an opening of approximately 150 nm, which had a depth of approximately 2500 nm (an aspect ratio was approximately 17), by PEALD-like process in a bottomless manner under the same conditions as in Reference Example 1 except that the deposition cycle was repeated 350 times (p=350) so that the film accumulated on the top surface of the substrate to a thickness of 160 nm.

The bottomless deposition has been confirmed by STEM photographs of cross-sectional views of trenches subjected to the bottomless deposition, which include (a) a view of a series of the film-deposited trenches, (b) an enlarged view of a top portion of one of the trenches, (c) an enlarged view of a bottom portion of the trench, and (d) an enlarged view of sidewalls of the trench. It has been confirmed that although the trenches are not fully filled with the film as observed in (a), the amorphous carbon polymer film is effectively flowable, wherein although the top portion of the trench is closed off with the film (the top is overfilled) as observed in (b), the film flows downward and extends along the sidewalls of the trench toward the bottom of the trench as observed in (d), without reaching the bottom of the trench as observed in (c), forming substantially conformal (substantially uniform thickness along the sidewalls) and homogenous film structures along the sidewalls.

Reference Example 3

An amorphous carbon polymer film was deposited on a Si substrate (having a diameter of 300 mm and a thickness of 0.7 mm) having trenches with an opening of approximately 140 to 160 nm, which had a depth of approximately 2500 nm (an aspect ratio was approximately 16 to 18), by PEALD-like process in a bottomless manner under the same conditions as in Reference Example 1 except that the deposition cycle was repeated 300 times (p=300) so that the film accumulated on the top surface of the substrate to a thickness of 116 nm.

FIG. 4 shows a schematic illustration of a STEM photograph of a cross-sectional view of the trench subjected to bottomless deposition (300 cycles) without ashing. As shown in FIG. 4, it was confirmed that although the trenches were not fully filled with the film, the amorphous carbon polymer film was effectively flowable, wherein although the top portion of the trench was just or barely closed off with the film (the top was overfilled) and although the film accumulated on the top surface of the substrate, the film flowed downward and extended along the sidewalls of the trench toward the bottom of the trench and slightly reached the bottom of the trench, forming substantially conformal (substantially uniform thickness along the sidewalls) and homogenous film structures along the sidewalls. The small deposition of the film at the bottom does not interfere with further etching to form an ultradeep hole, if dry etching conditions are set to have high selectivity (e.g., >100) of carbon film relative to the underlying layer, and thus, this deposition is still referred to as bottomless deposition. Further, by tuning the flowability of the film (slightly reducing the flowability), the flow of the film along the sidewalls can be stopped before reaching the bottom.

Example 3

An amorphous carbon polymer film was deposited on a Si substrate in a bottomless manner under the same conditions as in Reference Example 3. Thereafter, ashing was continuously conducted using a mixture of O₂ and Ar in the same manner as in Reference Example 1 except that RF time was shortened to 90 seconds so as to thin a portion of the film accumulated on the top surface of the substrate and remove a top closed portion (overfilled portion) of the film in the trenches to open the trenches, thereby forming a spacer-like structure in the trenches.

FIG. 5 shows a schematic illustration of a STEM photograph of a cross-sectional view of the trench subjected to bottomless deposition (300 cycles), followed by ashing (90 seconds). As shown in FIG. 5, it was confirmed that by ashing, the overfilled top portion of the trench was effectively removed so as to open the top of the trench without degrading CD integrity, forming substantially conformal (substantially uniform thickness along the sidewalls) and homogenous film structures along the sidewalls.

Reference Example 4

An amorphous carbon polymer film was deposited on a Si substrate in a bottomless manner under the same conditions as in Reference Example 3 except that the deposition cycle was repeated 350 times (p=350) so that the film accumulated on the top surface of the substrate to a thickness of 160 nm and completely closed the top opening of the trenches (the thickness of the overfilled portion above the trenches was 145 nm).

FIG. 6 shows a schematic illustration of a STEM photograph of a cross-sectional view of the trench subjected to bottomless deposition (350 cycles) without ashing. As shown in FIG. 6, it was confirmed that although the trench was not fully filled with the film, the amorphous carbon polymer film was effectively flowable, wherein although the top portion of the trench was closed off with the film and although the film accumulated on the top surface of the substrate, the film flowed downward and extended along the sidewalls of the trench toward the bottom of the trench in a manner similar to that in Reference Example 3.

Example 4

An amorphous carbon polymer film was deposited on a Si substrate in a bottomless manner under the same conditions as in Reference Example 4. Thereafter, ashing was continuously conducted using a mixture of O₂ and Ar in the same manner as in Reference Example 1 except that RF time was shortened to 90 seconds so as to thin a portion of the film accumulated on the top surface of the substrate and remove a top closed portion (overfilled portion) of the film in the trenches to open the trenches, thereby forming a spacer-like structure in the trenches (the thickness of the overfilled portion above the trenches was 95 nm).

FIG. 7 shows a schematic illustration of a STEM photograph of a cross-sectional view of the trench subjected to bottomless deposition (350 cycles), followed by ashing (90 seconds). As shown in FIG. 7, it was confirmed that by ashing, the overfilled top portion of the trench was effectively removed so as to open the top of each trench without degrading CD integrity, forming substantially conformal (substantially uniform thickness along the sidewalls) and homogenous film structures along the sidewalls.

It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention. 

I claim:
 1. A method of forming a topology-controlled layer on a patterned recess of a substrate, comprising: (i) depositing a Si-free C-containing film having filling capability on the patterned recess of the substrate by pulse plasma-assisted deposition to fill the recess in a bottom-up manner or bottomless manner; and (ii) subjecting the bottom-up or bottomless film filled in the recess to plasma ashing to remove a top portion of the filled film in a manner leaving primarily or substantially only a bottom portion of the filled film or primarily or substantially only a sidewall portion of the filled film.
 2. The method according to claim 1, wherein the plasma ashing in step (ii) is conducted using a direct or remote oxygen or hydrogen plasma.
 3. The method according to claim 2, wherein the direct or remote oxygen or hydrogen plasma is a direct or remote plasma of gas(es) selected from the group consisting of solely H₂, a mixture of Ar and H₂, a mixture of N₂ and H₂, a mixture of He and H₂, solely O₂, a mixture of O₂ and Ar, a mixture of O₂ and He, a mixture of O₂ and N₂.
 4. The method according to claim 1, wherein in step (i), the Si-free C-containing film is deposited using a hydrocarbon precursor.
 5. The method according to claim 1, wherein step (i) comprises: (ia) supplying a precursor to a reaction space where the substrate is placed, and (ib) exposing the patterned recess of the substrate to a plasma to deposit the Si-free C-containing film in the patterned recess, wherein step (ib) is conducted intermittently in a manner pulsing the plasma, and step (ia) is conducted continuously or intermittently without overlapping step (ib) as a step prerequisite for step (ib).
 6. The method according to claim 1, wherein the Si-free C-containing film is constituted substantially by hydrocarbons.
 7. The method according to claim 6, wherein plasma ashing is conducted to open the closed top portion of the recess and to leave primarily or substantially only the sidewall portion of the filled film in step (ii).
 8. The method according to claim 7, wherein step (i) continues until planarization of the film above the multiple recesses occurs, and plasma ashing is then conducted to make the surface topology of the film filled in the multiple recesses uniform, and to leave primarily or substantially only the bottom portion of the filled film in step (ii).
 9. The method according to claim 1, wherein an aspect ratio of the recess is in a range of 10 to 100, and a depth of the recess is more than 200 nm wherein the recess is filled with the film in a bottomless manner in step (i) and a top portion of the filled film closes a top opening of the recess.
 10. The method according to claim 1, wherein the substrate has multiple recesses having aspect ratios of 2 to 30 wherein the recesses are filled with the film in a bottom-up manner in step (i) wherein there are variations in surface topology due to the loading effect. 